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Advanced Thermodynamics and

Combustion
Thermodynamic Property Relations
(Module III)

Prof. Niranjan Sahoo

Department of Mechanical Engineering
Indian Institute of Technology Guwahati
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List of Topics

1. Thermodynamic Functions and Maxwell’s Equations

2. Property Relations for Phase Change Processes

3. Property Relations for Single Phase Systems

4. Heat Capacity Equations and its Applications

5. Joule – Thomson Coefficient and Liquefaction of Gases

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Lecture 12

Property Relations for Single Phase Systems

 Evaluation of Property Changes

 Temperature – Specific Volume Relation

 Temperature – Pressure Relation

 Internal Energy Equations

 Construction of Property Tables

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Evaluation of Property Change

• The fundamental thermodynamic functions provide a complete description of the
thermodynamic state. All properties of interest can be determined from the
thermodynamic functions by differentiation or combination.

• There are 16 property relations obtained by using the concepts of exact differential.

• The evaluation of changes in specific entropy, internal energy and enthalpy,

accompanying a phase change process is obtained through Clapeyron equation.
With suitable approximation, it reduces to Clausius – Clapeyron equation.

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Evaluation of Property Change

• The property relations can be considered single phase regions for pure substances.

• The changes in specific entropy, internal energy and enthalpy are considered
between two states in a single phase region. These expressions require both p-v-T
data and appropriate specific heat data.

• In a single phase region, any of the two parameters (p, v, T) can be regarded as
independent property to fix the state. The most appropriate choice are, (T, v) or (T, p).

• Some of the important property can be recalled: coefficient of volume expansion,

isothermal compressibility, isentropic compressibility and speed of sound.

• Many of these properties are the realistic behavior of the substance derived through
thermodynamic relations.

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Case I: Temperature – Specific Volume

• By considering temperature and specific volume as independent properties that fix
the state, the specific entropy is regarded as the function of these two parameter.

• Both temperature and specific volume can be varied independently so that one can
be varied keeping other constant.

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Case I: Temperature – Specific Volume

• A close look of expressions of “ds and du” revel that the change is associated with
sole dependence on p, v, T and cv .

• The first term of the expression requires the variation of cv with temperature at one
fixed specific volume (isometric). The integration of second term requires the
knowledge of p-v-T relation at states of interest. The accuracy of “ds and du” would
depend on the accuracy of the derivatives.

• When the integrands are to complicated in closed form, numerical approach may be
adopted to estimate “ds and du”.

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Case II: Temperature – Pressure

• By considering temperature and pressure as independent properties that fix the
state, the specific entropy is regarded as the function of these two parameter.

• Both temperature and pressure can be varied independently so that one can be
varied keeping other constant.

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Case II: Temperature – Pressure

• A close look of expressions of “ds and dh” revel that the change is associated with
sole dependence on p, v, T and cv .

• The first term of the expression requires the variation of cp with temperature at one
fixed specific volume (isometric). The integration of second term requires the
knowledge of p-v-T relation at states of interest. The accuracy of “ds and dh” would
depend on the accuracy of the derivatives.

• When the integrands are to complicated in closed form, numerical approach may be
adopted to estimate “ds and dh”.

• Note that the specific enthalpy and internal energy is related as h = u + pv which
means only one parameter needs to be found through integration.

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Internal Energy Equation

• The change in internal energy for a pure substance undergoing infinitesimal
reversible process can be obtained from T – ds relations.

• One relation is obtained when the properties u, s and p can be regarded as function
of T and v while other relation can be framed when u, s and v are considered as
function of T and p.

• Keeping volume constant, is difficult to achieve during an experiment, but it gives

straight forward calculation. So, the second case is a realistic approach.

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Construction of Property Tables

• Fundamentally, all properties of interest for a pure substance can be represented in
the functional form of measured data (p, v and T).

• In a typical T - v diagram, the enthalpy changes and entropy changes are of main
interest for a phase change and single phase regions. The internal energy change
can be obtained from enthalpy change data.

• Consider the eight states of the substance assigned as state points 1, 2, 3, 4, 5, 6, 7

& 8 each having own coordinates. Let us consider, how the values can be assigned
to each of these states based on property relations.

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Construction of Property Tables

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Numerical Problems
Q1. Derive the expressions for changes in internal energy with respect change in specific
volume, keeping temperature constant, for a gas an ideal gas and Van der Waals gas.

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Numerical Problems
Q2. Develop the expressions for changes in internal energy, entropy and enthalpy for a
gas undergoing change of pressures at constant temperature. Take the equation of state
as follows:

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THANK YOU

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